Preparation of conjugated diene polymers modified with an organo-tin or germanium halide

ABSTRACT

A process for producing a modified conjugated diene polymer which comprises the steps of (I) polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst comprising (a) a lanthanum series rare earth element compound, (b) an organoaluminum compound represented by the general formula, AlR 1  R 2  R 3  (wherein R 1 , R 2  and R 3  which may be same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R 1 , R 2  and R 3  is said hydrocarbon group) and, if necessary, at least one member selected from the group consisting of (c) a Lewis acid and/or (d) a Lewis base, and then (II) modifying the resulting reactive polymer with a modifying compound of the general formula, R 4   n  MX 4-n  (wherein R 4  is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin atom, X is a halogen atom, and n is an integer of 1 to 3).

This is a division of application Ser. No. 07/090,347, filed on Aug. 28, 1987 now U.S. Pat. No. 4,906,706.

BACKGROUND OF THE INVENTION

This invention relates to a novel process for producing a modified conjugated diene polymer having excellent wear resistance and excellent mechanical characteristics, by polymerizing a conjugated diene with a lanthanum series rare earth metal catalyst and reacting the resulting reactive polymer with a specific compound. This invention further relates to a novel modified conjugated diene polymer produced according to said process.

In recent years, requirements of higher durability and longer life for component rubbers are increasing. Hence, it has become necessary to improve rubbers in such characteristics as wear resistance, mechanical properties, heat generation and the like.

Polybutadienes (rubbery polymer) obtained using a catalyst composed mainly of nickel, cobalt, titanium, etc. have been poor in wear resistance.

Meanwhile, known rubbery polymers having excellent wear resistance are polybutadienes produced using a lanthanum series rare earth metal catalyst. Of these polybutadienes, one produced using a lanthanum series rare earth metal catalyst proposed by the present inventors in Japanese Patent Application Kokai (Laid-Open) No. 57410/1983 has particularly excellent wear resistance.

Japanese Patent Application Kokai (Laid-Open) No. 40109/1985 describes that the reaction between (a) a polybutadiene produced using a lanthanum series rare earth metal catalyst and (b) a tetrahalomethane alone or in admixture with a specific organoaluminum compound enables production of a polybutadiene with an improved processability.

However, these polybutadienes are yet insufficient in wear resistance.

FIELD OF THE INVENTION

This invention has been accomplished in order to solve the above-mentioned problems of the conventional techniques. This invention aims at providing a process for producing a modified conjugated diene polymer satisfying all of wear resistance, mechanical characteristics and low heat generation, as well as the modified conjugated diene polymer produced by said process.

Other objects and advantages of this invention will become apparent from the following description and accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings, FIG. 1 illustrates an example of the method for preparing the catalyst used in this invention;

FIG. 2 is a GPC chart of a polymer obtained in Example 8;

FIG. 3 is an IR absorption spectrum of the polymer;

FIG. 4 is a GPC chart of a polymer obtained in Comparative Example 4;

FIG. 5 is an IR absorption spectrum of the polymer;

FIG. 6 is a GPC chart of a polymer obtained in Example 9;

FIG. 7 is a GPC chart of a polymer obtained in Example 11;

FIG. 8 is a GPC chart of a polymer obtained in Example 13;

FIG. 9 is a GPC chart of a polymer obtained in Example 15;

FIG. 10 is an IR absorption spectrum of the polymer; and

FIG. 11 is a GPC chart of a polymer obtained in Example 16.

SUMMARY OF THE INVENTION

According to this invention, there is provided a process for producing a modified conjugated diene polymer which comprises the steps of (I) polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst comprising (a) a lanthanum series rare earth element compound, (b) an organoaluminum compound represented by the general formula, AlR¹ R² R³ (wherein R¹, R² and R³, which may be the same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R¹, R² and R³ is said hydrocarbon group) and, if necessary, (c) a Lewis acid and/or (d) a Lewis base and (II) reacting the resulting reactive polymer with a modifying compound selected from the group consisting of the following components (e), (f) and (g):

(e) an organometal halide compound represented by the general formula, R⁴ _(n) MX_(4-n) (wherein R⁴ is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin or germanium atom, X is a halogen atom, and n is an integer of 1 to 3),

(f) a heterocumulene compound or a three-membered heterocyclic compound having, in the molecule, a bond represented by the general formula, X¹ =Y=Z or ##STR1## (wherein X¹ is a carbon, nitrogen, oxygen or sulfur atom, Y is a carbon or sulfur atom, Z is a nitrogen, oxygen or sulfur atom, and X² is a nitrogen, oxygen or sulfur atom), (g) a halogenated compound having, in the molecule, a bond represented by the general formula, ##STR2## (wherein Y¹ is a nitrogen or oxygen atom, and X is a halogen atom).

This invention further provides the modified conjugated diene polymer thus produced.

According to this invention, various characteristics such as wear resistance, low heat generation, mechanical characteristics, etc. of a conjugated diene polymer, for example, polybutadiene can be improved by reacting a reactive polymer just produced by polymerizing a conjugated diene using a lanthanum series rare earth metal catalyst, with a specific compound.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The lanthanum series rare earth metal catalyst used in this invention is a catalyst system comprising (a) a lanthanum series rare earth metal compound [hereinafter referred to as the component (a)] and (b) an organoaluminum compound represented by the general formula, AlR¹ R² R³ [hereinafter referred to as the component (b)]. This catalyst system can further comprise, if necessary, (c) a Lewis acid [hereinafter referred to as the component (c)] and/or (d) a Lewis base [hereinafter referred to as the component (d)].

As the lanthanum series rare earth metal compound which is the component (a), there can be preferably used compounds represented by the general formula, LnY² ₃. Here, Ln is a lanthanum series rare earth element having an atomic number of 57 to 71 in the Periodic Table, and cerium, lanthanum, praseodyminum, neodyminum and gadolinium are preferred. Of these, neodymium is particularly preferred because of its easy commercial availability. These rare earth elements may be used alone or in admixture of at least two.

Y² is a hydrocarbon residue, an alkoxide residue, a thioalkoxide residue, an amide residue, a phosphoric acid salt residue, a phosphorous acid salt residue, a halide residue or a carboxylic acid salt residue. Of these, an alkoxide residue, a halide residue and a carboxylic acid salt residue are particularly preferred.

The hydrocarbon type compound of lanthanum series rare earth element includes compounds represented by the general formula, LnR₃ (wherein R is a hydrocarbon group of 1 to 20 carbon atoms, such as a benzyl group, a phenyl group, a butyl group, a cyclopentadienyl group or the like).

The alcohol type compound (alkoxide) includes compounds represented by the general formula, Ln(OR)₃ (wherein Ln and R have the same definitions as given previously). Preferred as the alcohol are 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, etc.

The thioalcohol type compound (thioalkoxide) includes compounds represented by the general formula, Ln(SR)₃ (wherein Ln and R have the same definitions as given previously). Preferred as the thioalcohol is thiophenol.

The amide type compound (amide) includes compounds represented by the general formula, Ln(NR₂)₃ (wherein Ln and R have the same definitions as given previously). Preferred as the amine are dihexylamine and dioctylamine.

The phosphoric acid salt of rare earth element includes compounds represented by the general formula, ##STR3## (wherein Ln has the same definition as given previously, and R and R' may be the same or different, R' has the same definition as that of R mentioned above). Preferred as the salt are neodymium tris(dihexyl phosphate) and neodymium tris(diphenyl phosphate).

The phosphorus acid salt of rare earth element includes compounds represented by the general formula, ##STR4## (wherein Ln, R and R' have the same definitions as given previously). Preferred as the salt are neodymium tris(dihexyl phosphite) and neodymium tris[di(ethylhexyl) phosphite].

The halide type compound includes compounds represented by the general formula, LnX₃ (wherein Ln has the same definition as given previously and X is a halogen atom). Preferred as the halogen atom are chlorine, bromine and iodine atoms.

The carboxylic acid salt of rare earth element includes compounds represented by the general formula, (RCOO)₃ Ln (wherein R is a hydrocarbon group of 1 to 20 carbon atoms, preferably a saturated or unsaturated alkyl group of straight, branched or cyclic chain, and the carboxyl group bonds to a primary, secondary or tertiary carbon atom). Preferred as the carboxylic acid are octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid and naphthenic acid.

Specific examples of the component (a) include neodymium trichloride, didymium trichloride (didymium is a rare earth metal mixture consisting of 72% by weight of neodymium, 20% by weight of lanthanum and 8% by weight of praseodymium), neodymium 2-ethylhexanoate, didymium 2-ethylhexanoate, neodymium naphthenate, neodymium 2,2-diethylhexanoate, neodymium trimethacrylate and polymers of neodymium trimethacrylate.

The organoaluminum compound which is the component (b) is a compound represented by the general formula, AlR¹ R² R³ (wherein R¹, R² and R³, which may be the same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms, and at least one of them is said hydrocarbon group). Specific examples of the component (b) include trimethylalminum, triethylaluminum, triisopropylalminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diisobutylaluminum hydride, diethylaliminum hydride, dipropylaluminum hydride, ethylalunimum dihydride, propylalumimum dihydride and isobutylaluminum dihydride.

The Lewis acid which is the component (c) includes, for example, aluminum halide compounds represented by the general formula, AlR⁵ _(m) S_(3-m) (wherein R⁵ is a hydrocarbon group of 1 to 8 carbon atoms, m is 0 or a positive number of 1 to 3, and X is a halogen atom), halogen atoms, and halides of tin, titanium and the like.

Of these, particularly preferred are dimethylaluminum chloride, diethylalunimum chloride, dibutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and bromides and iodides corresponding to them.

The Lewis base which is the component (d) includes acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorous compounds and mono- or di-hydric alcohols.

The lanthanum series rare earth metal catalyst used in this invention has the following conditions:

The mole ratio of the component (b)/the component (a) is preferably from 10 to 150, more preferably from 15 to 100. When the ratio is smaller than 10, the catalyst has a low polymerization activity. When the ratio is more than 150, the polymerization activity is not any more increased and such a high mole ratio is disadvantageous economically.

The mole ratio of the component (c)/the component (a) is preferably from 0 to 6, more preferably from 0.5 to 5.0. When the ratio exceeds 6, the polymerization activity tends to decrease.

The mole ratio of the component (d)/the component (a) is preferably from 0 to 20, more preferably from 1 to 15. When the ratio exceeds 20, the polymerization activity tends to decrease.

If necessary, the catalyst of this invention may further comprise, in addition to the components (a), (b), (c) and (d), a conjugated diene in an amount of 0 to 50 moles per mole of the lanthanum series rare earth metal compound which is the component (a). The conjugated diene used in preparation of the catalyst is the same as the monomer used in polymerization and may be isoprene, 1,3-butadiene, 1,3-pentadiene or the like. The conjugated diene as a catalyst component is not essential, but its use in the catalyst can noticeably enhance the activity of the catalyst.

The preparation of the catalyst if conducted, for example, by subjecting the components (a) to (d) dissolved in a solvent and, if necessary, the conjugated diene to reaction. In this case, the addition order of each component is not critical. It is preferable to previously mix these components and subject the mixture to reaction and aging from the standpoints of enhancement of polymerization activity and shortening the induction period for polymerization initiation. It is also possible to successively add the catalyst components directly to a mixture of a polymerization solvent and a monomer to be polymerized, during the polymerization.

An example of the preparation method of the catalyst used in this invention is illustrated in FIG. 1. As shown in FIG. 1, the lanthanum series rare earth metal catalyst used in this invention consists of (A) a lanthanum series rare earth metal compound (a) which is a transition metal component, (B) an organoaluminum compound (b) which is an organometal component, and, if necessary, (C) a Lewis acid (c) and/or a Lewis base (d), both of which are a third component, and the addition order of these components (a) to (d) in the preparation of the catalyst is not critical.

In the catalyst preparation, it is preferable to contact the component (a) with the component (d), though the addition order of the other components is not critical.

The polymerization solvent is an inert organic solvent. It includes aromatic hydrocarbons such as benzene, toluene, xylene and the like; aliphatic hydrocarbons such as n-pentane, n-hexane, n-butane, cyclohexane and the like; alicyclic hydrocarbons such as methylcyclopentane, cyclohexane and the like; and halogenated hydrocarbons such as ethylene dichloride, chlorobenzene and the like. These solvents can be used alone or in admixture of two or more.

The polymerization temperature is preferably -20° C. to 150° C., more preferably 30° to 120° C. The polymerization reaction can be conducted batchwise or continuously.

The monomer concentration in the polymerization solvent is preferably 5 to 50% by weight, more preferably 10 to 35% by weight.

In order for the lanthanum series rare earth metal catalyst and the formed polymer not to lose their activity during the polymerization, attention should be paid so that substances having a deactivating effect, such as oxygen, water and carbon dioxide cannot be introduced into the polymerization system.

In this invention, the organometal halide compound (e) to be allowed to react with the reactive polymer is represented by the general formula:

    R.sup.4.sub.n MX.sub.4-n

wherein R⁴ is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin or germanium atom, X is a halogen atom, and n is an integer of 1 to 3.

When M is a tin atom, the component (e) is, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, diphenyltin dichloride, dioctyltin dichloride, dibutyltin dichloride, phenyltin trichloride, butyltin trichloride or the like.

When M is a germanium atom, the component (e) is, for example, triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, butylgermanium trichloride or the like.

These components (e) can be co-used at any ratio.

The mole ratio of the component (e) to the component (a) is preferably from 0.1 to 100, more preferably from 0.5 to 50. When the mole ratio is less than 0.1, the modification reaction does not proceed sufficiently and, in addition, the improvement effect on wear resistance is insufficient. When the mole ratio exceeds 100, the improvement effect does not increase any further and, in some cases, toluene insolubles (gel) are formed.

The modification reaction is effected at a temperature of preferably 160° C. or less, more preferably 0° to 130° C., for a period of preferably 0.1 to 10 hours, more preferably 0.2 to 5 hours, with stirring.

In this invention, the heterocumulene compound to be allowed to react with the reactive polymer is a compound having a bond represented by the general formula:

    X.sup.1 =Y=Z

wherein X¹ is a carbon, nitrogen, oxygen or sulfur atom, Y is a carbon or sulfur atom, and Z is a nitrogen, oxygen or sulfur atom [this compound is hereinafter referred to as the component (f-1)].

The component (f-1) is a ketene compound when X¹ is a carbon atom, Y is a carbon atom and Z is an oxygen atom; a thioketene compound when X¹ is a carbon atom, Y is a carbon atom and Z is a sulfur atom; an isocyanate compound when X¹ is a nitrogen atom, Y is a carbon atom and Z is an oxygen atom; a thioisocyanate compound when X¹ is a nitrogen atom, Y is a carbon atom and Z is a sulfur atom; a carbodiimide compound when X¹ is a nitrogen atom, Y is a carbon abom and Z is a nitrogen atom; carbon dioxide when X¹ is an oxygen atom, Y is a carbon atom and Z is an oxygen atom; carbonyl sulfide when X¹ is an oxygen atom, Y is a carbon atom and Z is a sulfur atom; sulfur dioxide when X¹ is an oxygen atom, Y is a sulfur atom and Z is an oxygen atom; and carbon disulfide when X¹ is a sulfur atom, Y is a carbon atom and Z is a sulfur atom.

However, the component (f-1) is not restricted to these combinations.

Specific examples of the ketene compound are ethylketene, butylketene, phenylketene and toluylketene.

Specific examples of the thioketene compound are ethylthioketene, butylthioketene, phenylthioketene and toluylthioketene.

Specific examples of the isocyanate compound are phenyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, the polymeric type of diphenyl methane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.

Specific examples of the thioisocyanate compound are phenyl thioisocyanate, 2,4-tolylene dithioisocyanate and hexamethylene dithioisocyanate.

Specific examples of the carbodiimide compound are N,N'-diphenylcarbodiimide and N,N'-diethylcarbodiimide.

In this invention, the three-membered heterocyclic compound to be allowed to react with the reactive polymer is a compound having a bond represented by the general formula: ##STR5## wherein X² is a nitrogen, oxygen or sulfur atom [this compound is hereinafter referred to as the component (f-2)].

The component (f-2) is an ethyleneimine derivative when X² is a nitrogen atom; an epoxy compound when X² is an oxygen atom; and a thiirane compound when X² is a sulfur atom.

Specific examples of the ethyleneimine derivative are ethyleneimine, propyleneimine, N-phenylethyleneimine and N-(β-cyanoethyl)ethyleneimine.

Specific examples of the epoxy compound are ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil and epoxidized natural rubber.

Specific examples of the thiirane compound are thiirane, methylthiirane and phenylthiirane.

The mole ratio of the component (f) to the component (a) is preferably 0.1 to 200, more preferably 0.5 to 100. When the mole ratio is less than 0.1, the modification reaction does not proceed sufficiently and the improvement effect on wear resistance is insufficient. When the mole ratio exceeds 200, no further improvement effect is seen, and such a ratio is disadvantageous economically.

The modification reaction using the component (f-1) or (f-2) is effected at a temperature of preferably 160° C. or less, more preferably -30° C. to 130° C., for a period of preferably 0.1 to 10 hours, more preferably 0.2 to 5 hours, with stirring.

In this invention, the halogen compound (g) to be allowed to react with the reactive polymer has a bond represented by the general formula: ##STR6## wherein Y¹ is a nitrogen or oxygen atom and X is a halogen atom such as a chlorine atom, a bromine atom, an iodine atom or the like.

The component (g) has a bond ##STR7## when Y¹ is a nitrogen atom. Specific examples of such a compound are 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, 3,6-dichloro-4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6-dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2-(methylthio)pyrimidine, 2,4,5,6-tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6-dichloropyrazine, 2,4-bis(methylthio)-6-chloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 2-bromo-5-nitrothiazole, 2-chlorobenzothiazole and 2-chlorobenzoxazole.

The component (g) has a bond ##STR8## when Y¹ is an oxygen atom. Specific examples of such a compound are propionyl chloride, octanoyl chloride, stearyl chloride, beazoyl chloride, phthalyl chloride and maleyl chloride.

Preferred as the component (g) are 2,4,6-trichloro-1,3,5-triazine and benzoyl chloride.

The mole ratio of the component (g) to the component (a) is preferably 0.1 to 200, more preferably 0.5 to 100. When the mole ratio is less than 0.1, the modification reaction does not proceed sufficiently and the improvement effect on wear resistance is insufficient. When the mole ratio exceeds 200, no further improvement effect is seen and such a ratio is disadvantageous economically.

The modification reaction with the component (g) is effected at a temperature of preferably 160° C. or less, more preferably -30° C. to 130° C., for a period of preferably 0.1 to 10 hours, more preferably 0.2 to 5 hours, with stirring.

After the completion of the modification reaction, steam is blown into the polymer solution to remove the solvent, or a poor solvent is added to the polymer solution to coagulate the modified polymer. The modified polymer thus recovered is then dried using a hot roll or under reduced pressure to obtain the objective polymer. Alternatively, the solvent can be removed directly from the polymer solution under reduced pressure to obtain the objective polymer.

The modified conjugated diene polymer obtained in this invention is of a high cis-1,4 diene polymer. When it is a modified polybutadiene, the cis-1,4 content is 70% or more, preferably 80% or more. When it is a modified polyisoprene, the cis-1,4 content is 88% or more. In the case of a high cis-1,4 butadiene-isoprene copolymer, the cis-1,4 content in the butadiene unit is 80% or more and the cis-1,4 content in the isoprene unit is 88% or more.

The proportions of butadiene and isoprene in this copolymer can be varied freely.

The modified conjugated diene polymer obtained in this invention may have a molecular weight varying over a wide range. Its Mooney viscosity (ML₁₊₄, 100° C.) is preferably 10 to 120, more preferably 15 to 100 though not critical.

The modified conjugated diene polymer, when it is a copolymer, can be obtained as a block copolymer or a random copolymer depending upon the structure of the reactive polymer.

The structure of the modified conjugated diene polymer of this invention can be confirmed, for example, by infrared absorption spectrum based on absorption due to Sn-φ bond in the vicinity of 700 cm⁻¹, absorption due to Sn--CH₃ in the vicinity of 770 cm⁻¹ and the like.

When the diphenyltin dichloride is used as the component (e), the structure can be confirmed by the Fourier transform NMR spectrometer (hereinafter referred to as FT-NMR) using tetramethylsilane as the standard substance based on the peak in the vicinity of δ=7.4 ppm due to Sn-φ bond.

In the modified conjugated diene polymer of this invention, the structure that a functional group is added to the conjugated diene polymer chain can be confirmed by infrared absorption spectrum from absorption due to hydroxyl group in the vicinity of 3,600 cm⁻¹ when the modification is effected with a ketene compound, from absorption due to mercapto group in the vicinity of 2,600 cm⁻¹ when the modification is effected with a thioketene compound, from absorption band of amide II in the vicinity of 1,530 cm⁻¹ and absorption band of amide I in the vicinity of 1,680 cm⁻¹ when the modification is effected with an isocyanate compound and from absorption due to carboxylic acid or carboxylic acid salt in the vicinity of 1,700 cm⁻¹ when the modification is effected with carbon dioxide depending upon the after-treatment method.

When a modifying agent having a UV-active functional group such as a phenyl group or the like is used, the modification of polymer can easily be confirmed by use of GPC using a ultraviolet ray of 2.54 nm as a detector and a differential refractiometer together.

In the modified conjugated diene polymer of this invention, the structure that a functional group is added to the polymer chain can be confirmed by infrared absorption spectrum from absorption due to ##STR9## bond in the vicinity of 1,500-1,650 cm⁻¹ when the modification is effected with a compound having a ##STR10## bond or from absorption in the vicinity of 1,650-1,750 cm⁻¹ when the modification is effected with a compound having a ##STR11## bond.

In case the modifying component is not used, the molecular weight distribution of the resulting polybutadiene can not be determined by GPC using an ultraviolet ray of 254 nm as a detector.

However, when a phenyl group-containing compound, for example, is used as the modifying component, the molecular weight distribution of the resulting modified polymer determined by ultraviolet rays and the molecular weight distribution of the polymer determined by a differential refractometer can be correlated because of the presence of ultraviolet-ray absorption due to the phenyl group. From this correlation, the presence of the functional group in the modified polymer can be confirmed.

The modified conjugated diene polymer (I) of this invention can be used alone or in blend with 80% by weight or less of natural rubber (II) and/or other rubber (III) such as cis-1,4-polyisoprene, emulsion-polymerized styrene-butadiene copolymer, solution-polymerized styrene-butadiene copolymer, low cis-1,4-polybutadiene, high cis-1,4-polybutadiene, ethylenepropylene-diene copolymer, chloroprene, halogenated butyl rubber, NBR or the like. When it is used in blend, the blending ratio is preferably 20:80 to 90:10 in terms of weight ratio of (I):[(II)+(III)]. When the total content of (II) and (III) in the blend exceeds 80% by weight, the effect of this invention cannot be expected. The modified conjugated diene polymer of this invention or its blend can, if necessary, be extended with an aromatic, naphthenic or paraffinic oil and then mixed with conventional compounding agents for vulcanized rubber such as a filler (e.g. carbon black, silica, magnesium carbonate, calcium carbonate, glass fiber or the like), stearic acid, zinc white, an antioxidant, a vulcanizing accelerator and a vulcanizing agent, to form a rubber composition.

This rubber composition can be molded, vulcanized and then used in various applications such as tire (tread, undertread, carcass, side wall, bead), hose, belt, shoe sole, window frame, sealing material, rubber vibration insulator and other industrial applications.

This invention will be explained in more detail below referring to Examples, which are not by way of limitation but by way of illustration.

In the Examples, parts and % are by weight unless otherwise specified.

Various measurements in the Examples were made according to the following methods.

The reaction between a reactive polymer obtained by polymerization with a lanthanum series rare earth metal catalyst and a specific halogen compound was confirmed by examining the change of Mooney viscosity before and after the reaction, or by conducting a model reaction using a polymer having a number-average molecular weight of several thousands and subjecting the product to GPC and IR analysis.

Mooney viscosity

Measured according to JIS K 6300 (preheating: 1 minute; measurement: 4 minutes; and temperature: 100° C.).

Microstructure of polymer

Measured according to the IR absorption spectrum method (the Morero method).

The modified polymer obtained according to this invention was subjected to kneading with the following compounding recipe using a 230-cc Brabender and a 6-inch roll, and then the resulting compound was vulcanized at 145° C. for a predetermined period of time to obtain a vulcanizate. The vulcanizate was subjected to various measurements.

    ______________________________________                                         Compounding recipe                                                             ______________________________________                                         Polymer                 100    parts                                           Carbon black (HAF)      50     parts                                           Zinc white              3      parts                                           Stearic acid            2      parts                                           Antioxidant (810 NA*.sup.1)                                                                            1      part                                            Vulcanizing accelerator (TP*.sup.2)                                                                    0.8    part                                            Vulcanizing accelerator (MSA*.sup.3)                                                                   1      part                                            Sulfur                  1.5    parts                                           ______________________________________                                          *.sup.1 Nphenyl-Nisopropyl-p-phenylenediamine                                  *.sup.2 Sodium dibutyldithiocarbamate                                          *.sup.3 Noxydiethylene-2-benzothiazolesulfenamide                        

Tensile characteristics and hardness

Measured according to JIS K 6301.

Heat generation

Impact resilience (%) according to the Dunlop impact resilience test was used as a yardstick of heat generation. The measurement was made according to BS 903. A larger impact resilience (%) implies lower heat generation, which is desirable.

Abrasion

Measured according to ASTM D 2228 (the Pico method). A large Pico abrasion index implies superior abrasion resistance.

EXAMPLE 1

2.5 kg of cyclohexane and 500 g of 1,3-butadiene were placed in a reactor having an internal volume of 5 liters and equipped with a stirrer, in a nitrogen atmosphere. Separately, a catalyst was previously prepared by mixing (a) 0.93 mmol of neodymium 2-ethylhexanoate, (b) 27.7 mmol of triethylaluminum, (b) 10.2 mmol of diisobutylaluminum hydride, (c) 2.3 mmol of diethylaluminum chloride and (d) 1.85 mmol of acetylacetone in the presence of 4.6 mmol of 1,3-butadiene and aging the mixture at 40° C. for 30 minutes. This catalyst was added to the contents in the above reactor. The whole mixture was subjected to adiabatic reaction at 70° C. for 1.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. In order to measure the Mooney viscosity of the formed polybutadiene, a part of the polymerization mixture was taken out, coagulated and dried. The drying product (polymer) had a Mooney viscosity of 49.

The polymerization mixture was cooled to 60° C. Thereto was added (e) 2.33 mmol of diphenyltin dichloride. The mixture was stirred for 30 minutes. Then, 3.0 g of 2,6-di-t-butyl-p-cresol was added. Steam was blown into the mixture for coagulation. The coagulation product was dried using a hot roll of 100° C. The modified poly(1,3-butadiene) thus obtained had such a microstructure that the cis-1,4 content was 97.3%, the trans-1,4 content was 1.3% and the vinyl content was 1.4%. Its Mooney viscosity was 64.

The evaluation results on the properties of the vulcanizate of the above modified poly(1,3-butadiene) are shown in Table 1.

COMPARATIVE EXAMPLES 1 AND 2

Comparative Example 1 is a case where no diphenyltin dichloride was used in Example 1. Comparative Example 2 is a case where a commercially available polybutadiene (BR-01 manufactured by Japan Synthetic Rubber Co., Ltd.) was vulcanized to obtain a vulcanizate. The evaluation results on the properties of the two vulcanizates are shown in Table 1.

As is appreciated from the comparison of Example 1 with Comparative Examples 1 and 2, the modified conjugated diene polymer of this invention obtained by reacting the reactive polymer just after polymerization using the lanthanum series rare earth metal catalyst, with diphenyltin dichloride has remarkably improved abrasion resistance.

EXAMPLES 2 TO 7

Example 2 is a case where the amount of diphenyltin dichloride used was increased as compared with Example 1. Examples 3 and 7 are cases where triphenyltin chloride was used in place of the diphenyltin dichloride in Example 1. Examples 4 and 5 are cases where phenyltin trichloride was used in place of the diphenyltin dichloride in Example 1. Example 6 is a case where dibutyltin dichloride was used in place of the diphenyltin dichloride in Example 1.

The evaluation results on the properties of each vulcanizate are shown in Table 1.

COMPARATIVE EXAMPLE 3

A poly(1,3-butadiene) was produced in the same manner as in Example 1, except that carbon tetrachloride was used in place of the diphenyltin dichloride. The results of polymerization and the evaluation results on the properties of the vulcanizate are shown in Table 1.

                                      TABLE 1                                      __________________________________________________________________________                          Comparative                                                                           Comparative                                                       Example 1                                                                            Example 1                                                                             Example 2                                                                             Example 2                                                                            Example 3                             __________________________________________________________________________     Type of organometal halide                                                                    φ.sub.2 SnCl.sub.2                                                               Not Used                                                                              --     φ.sub.2 SnCl.sub.2                                                               φ.sub.3 SnCl                      [component (e)]                                                                Mole ratio of component (e)/                                                                  2.5   --     --     5.0   10.0                                  component (a)                                                                  Mooney viscosity before and                                                    after addition of component (e)                                                Before addition                                                                               49    51     (44)   54    77                                    After addition 64    --            65    86                                    Microstructure (%)                                                             Cis-1,4 content                                                                               97.3  96.6   95.3   96.8  96.9                                  Trans-1,4 content                                                                             1.3   1.5    2.1    1.4   1.3                                   Vinyl content  1.4   1.9    2.6    1.8   1.8                                   Properties of vulcanizate                                                      Tensile characteristics                                                        200% modulus (kgf/cm.sup.2)                                                                   106   97     92     112   115                                   300% modulus (kgf/cm.sup.2)                                                                   171   158    140    178   176                                   Tensile strength (kgf/cm.sup.2)                                                               217   221    192    218   220                                   Elongation at break (%)                                                                       380   410    390    370   370                                   Hardness (JIS A)                                                                              73    73     71     75    75                                    Dunlop impact resilience (%)                                                   Room temperature                                                                              63    64     59     66    67                                    50° C.  66    65     60     66    67                                    80° C.  67    66     63     67    69                                    Pico abrasion index*                                                                          129   107    100    123   120                                   __________________________________________________________________________                                             Comparative                                           Example 4                                                                            Example 5                                                                            Example 6                                                                             Example 7                                                                            Example 3                              __________________________________________________________________________     Type of organometal halide                                                                    φSnCl.sub.3                                                                      φSnCl.sub.3                                                                      (n-Bu).sub.2 SnCl.sub.2                                                               φ.sub.3 SnCl                                                                     CCl.sub.4                              [component (e)]                                                                Mole ratio of component (e)/                                                                  1.7   3.3   5.0    30    25                                     component (a)                                                                  Mooney viscosity before and                                                    after addition of component (e)                                                Before addition                                                                               51    54    48     25    48                                     After addition 52    55    61     48    48                                     Microstructure (%)                                                             Cis-1,4 content                                                                               97.0  97.3  96.4   96.4  96.3                                   Trans-1,4 content                                                                             1.3   1.4   1.7    1.8   1.7                                    Vinyl content  1.7   1.3   1.9    1.8   2.0                                    Properties of vulcanizate                                                      Tensile characteristics                                                        200% modulus (kgf/cm.sup.2)                                                                   97    100   115    98    96                                     300% modulus (kgf/cm.sup.2)                                                                   157   162   183    155   159                                    Tensile strength (kgf/cm.sup.2)                                                               205   209   221    201   220                                    Elongation at break (%)                                                                       400   390   380    360   400                                    Hardness (JIS A)                                                                              73    75    74     73    73                                     Dunlop impact resilience (%)                                                   Room temperature                                                                              63    65    67     66    63                                     50° C.  64    66    67     66    64                                     80°  C. 66    68    68     67    65                                     Pico abrasion index*                                                                          126   126   127    116   106                                    __________________________________________________________________________      Note:                                                                          *In this measurement, the abrasion loss of a vulcanizate of a commerciall      available polybutadiene JSR BR01 measured according to the same Pico           method was taken as a reference index of 100.                            

EXAMPLE 8

60 g of cyclohexane and 6 g of 1,3-butadiene were placed in a pressure bottle having an internal volume of 100 ml in a nitrogen atmosphere. Separately, a catalyst was previously prepared by mixing (a) 0.111 mmol of neodymium 2-ethylhexanoate, (b) 3.11 mmol of triethylaluminum, (b) 1.55 mmol of diisobutylaluminum hydride, (c) 0.222 mmol of diethylaluminum chloride and (d) 0.222 mmol of acetylacetone in the presence of 0.555 mmol of 1,3-butadiene, and aging the mixture at 40° C. for 30 minutes. This catalyst was added to the contents in the above pressure bottle. The whole mixture was subjected to adiabatic reaction at 60° C. for 1 hour. The polymerization conversion of 1,3-butadiene was almost 100%.

To the polymerization mixture was added 0.74 mmol of (f) the polymeric type of diphenylmethane diisocyanate [PAPI-135 manufactured by MD Kasei K.K. (hereinafter referred to as C-MDI)].

The mixture was stirred for 1 hour and then coagulated with methanol. The resulting modified polymer was dissolved in toluene and the solution was coagulated with methanol. This procedure was repeated three times to completely remove the unreacted C-MDI. The resulting polymer was dried at room temperature under reduced pressure.

The thus obtained modified poly(1,3-butadiene) had such a microstructure that the cis-1,4 content was 97.0%, the trans-1,4 content was 1.5% and the vinyl content was 1.5%.

The GPC chart of this modified polymer is shown in FIG. 2.

As is clear from FIG. 2, both the molecular weight distribution determined by a differential refractometer and the molecular weight distribution determined by an ultraviolet ray of 254 nm appear in correlation to GPC count, and the UV absorption spectrum shows higher absorption intensities at lower molecular weights and correlates to the number of polymer terminals.

The IR absorption spectrum of the modified polymer is shown in FIG. 3. As is clear from FIG. 3, an amide II absorption band appears in the vicinity of 1,520 cm⁻¹ and an amide I absorption band appears in the vicinity of 1,690 cm⁻¹ ; thus, C-MDI has been added to the polymer as a result of reaction.

The proportion of functional group added per chain of polymer was determined by a titration method and a polystyrene-reduced number-average molecular weight to be 45%.

COMPARATIVE EXAMPLE 4

A poly(1,3-butadiene) was obtained in the same manner as in Example 8, except that C-MDI as the component (f) was not used.

The GPC chart and the IR absorption spectrum of the polymer are shown in FIG. 4 and FIG. 5, respectively.

As is appreciated from the comparison of Example 8 and Comparative Example 4, the modified polymer of this invention has a high cis-1,4 content and contains a functional group as a result of addition reaction; thus, it is a novel polymer different from conventional polymers.

EXAMPLE 9

The procedure of Example 8 was repeated, except that phenyl isocyanate as a component (f-1) was used in place of the C-MDI of Example 8 to effect polymer modification.

The GPC chart of the modified polymer obtained is shown in FIG. 6. The presence of functional group in modified polymer is recognized from FIG. 6.

The proportion of functional group added per polymer chain was 53%.

EXAMPLE 10

A modified poly(1,3-butadiene) was obtained in the same manner as in Example 8, except that the amount of C-MDI was increased to 2.96 mmol.

In the modified polymer obtained, the UV absorption in GPC chart increased and the proportion of functional group added per polymer chain was 68%.

EXAMPLE 11

A modified poly(1,3-butadiene) was obtained in the same manner as in Example 8, except that no triisobutylaluminum was used and 16.7 mmol of carbon disulfide was used in place of the C-MDI as the component (f-1).

The GPC chart of the modified polymer obtained is shown in FIG. 7.

FIG. 7 indicates the presence of UV absorption and accordingly the addition of carbon dioxide.

EXAMPLE 12

2.5 kg of cyclohexane and 500 g of 1,3-butadiene were placed in a reactor having an internal volume of 5 liters and equipped with a stirrer, in a nitrogen atmosphere. Separately, a catalyst was previously prepared by mixing (a) 0.93 mmol of neodymium 2-ethylhexanoate, (b) 27.7 mmol of triethylaluminum, (b) 10.2 mmol of diisobutylaluminum hydride, (c) 2.3 mmol of diethylaluminum chloride and (d) 1.85 mmol of acetylacetone in the presence of 4.6 mmol of 1,3-butadiene and aging the mixture at 40° C. for 30 minutes. This catalyst was added to the contents in the above reactor. The whole mixture was subjected to adiabatic reaction at 70° C. for 1.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. For measurement of Mooney viscosity, a part of the polymerization mixture was taken out, coagulated and dried. The drying product [poly(1,3-butadiene)] had a Mooney viscosity of 30.

The polymerization mixture was cooled to 60° C. Thereto was added 5.1 mmol of C-MDI as the component (f-1). The mixture was stirred for 1 hour.

Then, 3.0 g of 2,6-di-t-butyl-p-cresol was added. The resulting mixture was coagulated using steam. The coagulation product was dried using a hot roll of 100° C. The thus obtained modified poly(1,3-butadiene) had such a microstructure that the cis-1,4 content was 97.8%, the trans-1,4 content was 1.0% bond and the vinyl content was 1.2%. It had a Mooney visocsity of 38.

The evaluation results on the properties of the vulcanizate of the modified polymer are shown in Table 2.

COMPARATIVE EXAMPLE 5

A poly(1,3-butadiene) was obtained in the same manner as in Example 12, except that no C-MDI as the component (f-1) was used.

The microstructure of the polymer obtained as well as the evaluation results on the properties of the vulcanizate of the polymer obtained is shown in Table 2.

COMPARATIVE EXAMPLE 6

The properties of a vulcanizate of a commercially available polybutadiene (Polybutadiene BR-01 manufactured by Japan Synthetic Rubber Co., Ltd.) are shown in Table 2.

As is clear from Table 2, the modified polymer of this invention obtained by reacting C-MDI with the reactive polymer just after the polymerization using the lanthanum series rare earth metal catalyst are greatly improved in wear resistance, heat generation and tensile strength.

EXAMPLE 13

Modification of poly(1,3-butadiene) was effected in the same manner as in Example 11, except that 16.7 mmol of styrene oxide as the component (f-2) was used in place of the carbon disulfide as the component (f-1). The GPC chart of the modified polymer obtained is shown in FIG. 8. It is seen from FIG. 8 that there is UV absorption and accordingly the addition of styrene oxide as a result of its reaction with poly(1,3-butadiene).

EXAMPLE 14

A modified poly(1,3-butadiene) was obtained in the same manner as in Example 12, except that 15.3 mmol of carbon disulfide was used in place of the C-MDI of Example 12.

The polymerization results and the properties of the vulcanizate of the modified polymer obtained are shown in Table 2.

COMPARATIVE EXAMPLE 7

A polymer was produced in the same manner as in Example 12, except that 5.1 mmol of carbon tetrachloride was used in place of the C-MDI as the component (f-1).

The polymerization results and the properties of the vulcanizate of the modified polymer obtained are shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                    Example                                                                             Comparative                                                                           Comparative                                                                           Example                                                                             Comparative                                            12   Example 5                                                                             Example 6                                                                             14   Example 7                               __________________________________________________________________________     Type of modifying component                                                                   C-MDI                                                                               Not used                                                                              --     CS.sub.2                                                                            CCl.sub.4                               Mooney viscosity before and                                                    after addition of modifying                                                    component                                                                      Before addition                                                                               30   32     44     35   40                                      After addition 38   --     --     40   40                                      Microstructure (%)                                                             Cis-1,4 content                                                                               97.8 97.4   95.3   97.1 96.5                                    Trans-1,4 content                                                                             1.0  1.2    2.1    1.8  1.8                                     Vinyl content  1.2  1.3    2.6    1.1  1.7                                     Properties of vulcanizate                                                      Tensile characteristics                                                        200% modulus (kgf/cm.sup.2)                                                                   112  96     91     118  95                                      300% modulus (kgf/cm.sup.2)                                                                   175  155    138    183  158                                     Tensile strength (kgf/cm.sup.2)                                                               242  214    195    248  217                                     Elongation at break (%)                                                                       420  390    400    380  400                                     Hardness (JIS A)                                                                              73   73     70     73   73                                      Dunlop impact resilience (%)                                                   Room temperature                                                                              65   61     58     65   62                                      50° C.  67   63     60     68   63                                      80° C.  69   65     62     69   64                                      Pico abrasion index*                                                                          135  108    100    130  107                                     __________________________________________________________________________      Note:                                                                          *In this measurement, the abrasion loss of a commercially available            polybutadiene JSR ER01 measured according to the same Pico method was          taken as a reference index of 100.                                       

EXAMPLE 15

The procedure of Example 8 was repeated, except that 3.33 mmol of 2,4,6-trichloro-1,3,5-triazine (hereinafter referred to as TCT) as the component (f) was used in place of the C-MDI to effect polymer modification.

The modified poly(1,3-butadiene) thus obtained had such a microstructure that the cis-1,4 content was 97.4%, the trans-1,4 content was 1.2% and the vinyl content was 1.4%.

The GPC chart of the modified polymer is shown in FIG. 9.

As is clear from FIG. 9, the molecular weight distribution determined by a differential refractometer and the molecular weight distribution determined by an ultraviolet ray of 254 nm appear in correlation to GPC count, and the UV absorption spectrum shows higher absorption intensities on the lower molecular weight side and correlates to the number of polymer terminals.

The IR absorption spectrum of the modified polymer is shown in FIG. 10. As is clear from FIG. 10, an absorption spectrum based on 1,3,5-triazine ring appears in the vicinity of 1,540 cm⁻¹, which indicates that TCT was added to the polymer chain as a result of reaction.

EXAMPLE 16

A modified poly(1,3-butadiene) was produced in the same manner as in Example 15, except that benzoyl chloride as the component (g) was used in place of the TCT.

The GPC chart of the modified polymer obtained is shown in FIG. 11, which indicates that functional groups have been added to polymer chain.

EXAMPLE 17

2.5 kg of cyclohexane and 350 g of 1,3-butadiene were placed in a reactor having an internal volume of 5 liters and equipped with a stirrer, in a nitrogen atmosphere. Separately, a catalyst was previously prepared by mixing (a) 0.43 mmol of neodymium 2-ethylhexanoate, (b) 12.1 mmol of triethylaluminum, (b) 9.5 mmol of diisobutylaluminum hydride, (c) 0.56 mmol of diethylaluminum chloride and (d) 0.86 mmol of acetylacetone in the presence of 4.6 mmol of 1,3-butadiene and aging the mixture at 40° C. for 30 minutes. This catalyst was added to the contents in the above reactor. The whole mixture was subjected to adiabatic reaction at 70° C. for 1.5 hours. The polymerization conversion of 1,3-butadiene was almost 100%. For Mooney viscosity measurement, a part of the polymerization mixture was taken out, coagulated and dried. The polymer obtained had a Mooney viscosity of 31.

The polymerization mixture was cooled to 60° C. Thereto was added 2.88 mmol of TCT as the component (g). The resulting mixture was stirred for 1 hour.

Then, 2.1 g of 2,6-di-t-butyl-p-cresol was added. The mixture was coagulated using steam. The coagulation product was dried using a hot roll of 100° C. The modified poly(1,3-butadiene) thus obtained had such a microstructure that the cis-1,4 content was 97.8%, the trans-1,4 content was 1.8% and the vinyl content was 1.2%. The polymer had a Mooney viscosity of 37.

The evaluation results on the properties of the vulcanizate of the modified polymer are shown in Table 3.

EXAMPLE 18

A modified poly(1,3-butadiene) was produced in the same manner as in Example 17, except that 8.6 mmol of benzoyl chloride was used in place of the TCT as the component (g). The microstructure of the modified polymer obtained and the evaluation results on the properties of the vulcanizate of the modified polymer are shown in Table 3.

                  TABLE 3                                                          ______________________________________                                                           Example 17                                                                             Example 18                                           ______________________________________                                         Type of modifying component                                                                        TCT       Benzoyl                                                                        chloride                                         Mooney viscosity before and after                                              addition of modifying component                                                Before addition     31        28                                               After addition      37        31                                               Microstructure (%)                                                             Cis-1,4 content     97.0      97.2                                             Trans-1,4 content   1.8       1.4                                              Vinyl content       1.2       1.4                                              Properties of vulcanizate                                                      Tensile characteristics                                                        200% modulus (kgf/cm.sup.2)                                                                        118       102                                              300% modulus (kgf/cm.sup.2)                                                                        183       164                                              Tensile strength (kgf/cm.sup.2)                                                                    255       224                                              Elongation at break (%)                                                                            480       450                                              Hardness (JIS A)    72        71                                               Dunlop impact resilience (%)                                                   Room temperature    65        65                                               50° C.       68        67                                               80° C.       69        68                                               Pico abrasion index*                                                                               141       128                                              ______________________________________                                          Note:                                                                          *In this measurement, the abrasion loss of a vulcanizate of a commerciall      available JSR BR01 measured according to the same Pico method was taken a      a reference index of 100.                                                

EXAMPLE 19

The modified polymer (polymer A) obtained in accordance with Example 1, having a Mooney viscosity of 57 and having a cis-1,4 content of 97.1%, a trans-1,4 content of 1.5% and a vinyl content of 1.4% was blended with a natural rubber in the blending ratio shown in Table 4. The blend was vulcanized with the compounding recipe shown previously.

The properties of the vulcanizate are shown in Table 4.

EXAMPLES 20 TO 22 AND COMPARATIVE EXAMPLES 8 AND 9

Vulcanization was conducted in the same manner as in Example 19, except that the polymer A (see Table 5) was replaced by the following polymers B to F (see Table 5). The properties of each vulcanizate are shown in Table 4.

Polymer B: A modified polymer obtained in the same manner as mentioned above for the polymer A, except that triphenyltin chloride was used in place of the diphenyltin dichloride.

Polymer C: A modified polymer obtained in the same manner as mentioned above for the polymer A, except that phenyltin trichloride was used in place of the diphenyltin dichloride.

Polymer D: A modified polymer obtained in the same manner as mentioned above for the polymer A, except that dibutyltin dichloride was used in place of the diphenyltin dichloride.

Polymer E: An unmodified polymer obtained in the same manner as mentioned above for the polymer A, except that no modification with diphenyltin dichloride was conducted.

Polymer F: A polymer obtained in the same manner as mentioned above for the polymer A, except that the diphenyltin dichloride was replaced by carbon tetracloride.

COMPARATIVE EXAMPLES 10 AND 11

Vulcanization was conducted in the same manner as in Example 19, except that a commercially available polybutadiene rubber (JSR BR 01 manufactured by Japan Synthetic Rubber Co., Ltd.) was used in place of the polymer A. The properties of each vulcanizate are shown in Table 4.

From the comparison of Examples 19 and 22 with Comparative Examples 8 to 11, it is clear that the rubber compositions of this invention have excellent wear resistance, good mechanical strengths and low heat generation characteristic.

COMPARATIVE EXAMPLE 12

Vulcanization was conducted in the same manner as in Example 19, except that the blending ratio of the polymer A to the natural rubber was changed to 10:90. The properties of the vulcanizate obtained are shown in Table 4, which indicates that the effect of this invention cannot be expected when the rubber composition contains a too small amount of the polymer A.

                                      TABLE 4                                      __________________________________________________________________________                          Comparative                                                                           Comparative                                                                           Comparative                                                Example 19                                                                           Example 8                                                                             Example 9                                                                             Example 10                                                                            Example 20                           __________________________________________________________________________     Type of polymer (parts)                                                        Polymer A      50                                                              Polymer B                                 30                                   Polymer C                                                                      Polymer D                                                                      Polymer E            50                                                        Polymer F                   50                                                 JSR-BR01                           50                                          Natural rubber (RSS No. 3)                                                                    50    50     50     50     70                                   Properties of vulcanizate                                                      Tensile characteristics                                                        300% modulus (kgf/cm.sup.2)                                                                   121   113    106    114    125                                  Tensile strength (kgf/cm.sup.2)                                                               262   251    248    254    274                                  Elongation at break (%)                                                                       520   530    490    500    480                                  Hardness (JIS A)                                                                              63    63     64     65     64                                   Dunlop impact resilience (%)                                                   Room temperature                                                                              59    56     56     55     54                                   50° C.  62    58     59     57     56                                   80° C.  63    60     61     59     58                                   Pico abrasion index*                                                                          125   108    106    100    118                                  __________________________________________________________________________                                       Comparative                                                                           Comparative                                                 Example 21                                                                           Example 22                                                                           Example 11                                                                            Example 12                            __________________________________________________________________________            Type of polymer (parts)                                                        Polymer A                         10                                           Polymer B      70                                                              Polymer C            70                                                        Polymer D                                                                      Polymer E                                                                      Polymer F                                                                      JSR-BR01                   70                                                  Natural rubber (RSS No. 3)                                                                    30    30    30     90                                           Properties of vulcanizate                                                      Tensile characteristics                                                        300% modulus (kgf/cm.sup.2)                                                                   109   110   106    145                                          Tensile strength (kgf/cm.sup.2)                                                               231   225   227    295                                          Elongation at break (%)                                                                       520   510   490    450                                          Hardness (JIS A)                                                                              63    64    65     64                                           Dunlop impact resilience (%)                                                   Room temperature                                                                              60    60    59     53                                           50° C.  63    62    61     54                                           80° C.  66    65    64     55                                           Pico abrasion index*                                                                          132   135   105    94                                    __________________________________________________________________________      Note:                                                                          *In this measurement, the abrasion loss of a vulcanizate of a rubber           composition [50% by weight of a polybutadiene rubber (JSR BR01) and 50% b      weight of a natural rubber (RSS No. 3)] measured according to the same         Pico method was taken as a reference index of 100.                       

                                      TABLE 5                                      __________________________________________________________________________                    Polymer                                                                             Polymer                                                                             Polymer                                                                             Polymer                                                                               Polymer                                                                             Polymer                                             A    B    C    D      D    F                                    __________________________________________________________________________     Type of modifying component                                                                   φ.sub.2 SnCl.sub.2                                                              φ.sub.3 SnCl                                                                    φSnCl.sub.3                                                                     (n-Bu).sub.2 SnCl.sub.2                                                               Not used                                                                            CCl.sub.4                            Mole ratio of modifying                                                                       2.5  15   5    10     --   30                                   component/component (a)                                                        Mooney viscosity before and                                                    after addition of modifying                                                    component                                                                      Before addition                                                                               43   35   32   28     43   46                                   After addition 57   42   48   41     --   46                                   Microstructure (%)                                                             Cis-1,4 content                                                                               97.1 97.0 96.8 97.3   96.9 96.8                                 Trans-1,4 content                                                                             1.5  1.6  1.4  1.5    1.4  1.4                                  Vinyl content  1.4  1.4  1.8  1.2    1.7  1.8                                  __________________________________________________________________________ 

What is claimed is:
 1. A process for producing a modified conjugated diene polymer which comprises the steps of (I) polymerizing a conjugated diene in an inert organic solvent in the presence of a catalyst comprising (a) a lanthanum series rare earth metal compound, (b) an organoaluminum compound represented by the general formula, AlR¹ R² R³ (wherein R¹, R² and R³, which may be same or different, are hydrogen atoms or hydrocarbon groups of 1 to 8 carbon atoms and at least one of R¹, R² and R³ is said hydrogencarbon group) and, if necessary, (c) a Lewis acid and/or (d) a Lewis base and (II) modifying the resulting reactive polymer with a modifying compound of an organometal halide compound represented by the general formula, R⁴ _(n) MX_(4-n) (wherein R⁴ is an alkyl group of 1 to 20 carbon atoms or an aryl group, M is a tin atom, X is a halogen atom, and n is an integer of 1 to 3),
 2. A process according to claim 1, wherein the conjugated diene is 1,3-butadiene, isoprene or a mixture thereof.
 3. A process according to claim 1, wherein the lanthanum series rare earth element compound (a) is a compound represented by the general formula, LnY² ₃ (wherein Ln is at least one lanthanum series rare earth element having an atomic number of 57 to 71 and Y² is a hydrocarbon residue, an alkoxide residue, a thioalkoxide residue, an amide residue, a phosphoric acid salt residue, a phosphorous acid salt residue or a carboxylic acid salt residue.
 4. A process according to claim 3, wherein the Ln is at least one member selected from the group consisting of cerium, preseodymium, neodymium and gadolinium.
 5. A process according to claim 3, wherein the Ln is neodymium.
 6. A process according to claim 3, wherein the LnY² ₃ compound is a compound represented by the general formula, LnR₃, Ln(OR)₃, Ln(SR)₃, Ln(NR₂)₃, ##STR12## LnX₃ or (RCOO)₃ Ln (wherein Ln has the same definition as given above, R and R', which may be same or different, are hydrocarbon groups of 1 to 20 carbon atoms, and X is a halogen atom).
 7. A process according to claim 3, wherein the lanthanum series rare earth element compound (a) is selected from the group consisting of neodymium trichloride, didymium trichloride (the didymium is a rare earth metal mixture consisting of 72% by weight of neodymium, 20% by weight of lanthanum and 8% by weight of praseodymium), neodymium 2-ethylhexanoate, didymium 2-ethylhexanoate, neodymium naphthenate, neodymium 2,2-diethylhexanoate, neodymium trimethacrylate and polymers of neodymium trimethacrylate.
 8. A process according to claim 1, wherein the organoaluminum compound (b) is trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diisobutylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride or isobutylaluminum dihydride.
 9. A process according to claim 1, wherein the Lewis acid (c) is selected from the group consisting of aluminum halide compounds represented by the general formula, AlR⁵ _(m) X_(3-m) (wherein R⁵ is a hydrocarbon group having 1 to 8 carbon atoms, m is 0 or a positive number of 1 to 3, and X is a halogen atom), halogen elements, tin halides and titanium halides.
 10. A process according to claim 1, wherein the Lewis acid (c) is selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and bromides and iodides corresponding to them.
 11. A process according to claim 1, wherein the Lewis base (d) is selected from the group consisting of acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorus compounds and mono- or dihydric alcohols.
 12. A process according to claim 1, wherein the mole ratio of the component (b)/the component (a) is 10 to
 150. 13. A process according to claim 1, wherein the mole ratio of the component (b)/the component (a) is 15 to
 100. 14. A process according to claim 12, wherein the catalyst consists of the component (a) and the component (b).
 15. A process according to claim 12, wherein the mole ratio of the component (c)/the component (a) is from 0 to
 6. 16. A process according to claim 13, wherein the mole ratio of the component (c)/the component (a) is from 0.5 to 5.0.
 17. A process according to claim 12, wherein the mole ratio of the component (d)/the component (a) is from 0 to
 20. 18. A process according to claim 13, wherein the mole ratio of the component (d)/the component (a) is from 1 to
 15. 19. A process according to claim 1, wherein the catalyst is prepared previously by mixing the components (a) to (d) in the presence or absence of a conjugated diene in a polymerization solvent, subjecting the mixture to reaction and then aging the reaction mixture.
 20. A process according to claim 19, wherein the polymerization solvent is at least one member selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons.
 21. A process according to claim 1, wherein the polymerization in the step (I) is conducted at -20° C. to 150° C.
 22. A process according to claim 20, wherein the monomer concentration in the solvent is 5 to 50% by weight.
 23. A process according to claim 1, wherein the modification in the step (II) is conducted at 160° C. or less for 0.1 to 10 hours with stirring.
 24. A process according to claim 1, wherein the organotin halide compound is triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, diphenyltin dichloride, dioctyltin dichloride, dibutyltin dichloride, phenyltin trichloride or butyltin trichloride.
 25. A process according to claim 1, wherein the mole ratio of the organometal halide/the compound (a) is from 0.1 to
 100. 